DE102007047212A1 - Curable silicone compositions - Google Patents

Abstract

The present invention relates to thermally hydrosilylation crosslinkable silicone compositions, processes for their preparation, platinum catalysts used for this purpose and the use of crosslinkable compositions.

Description

The The present invention relates to thermal hydrosilylation Crosslinkable silicone compositions, process for their preparation, For this purpose used platinum catalysts and the use of crosslinkable Compositions.

Around addition-curing silicone compositions by the hydrosilylation reaction To crosslink, a catalyst is generally used, the typically contains platinum or a platinum group metal. In the catalytic reaction are aliphatically unsaturated Groups reacted with Si-bonded hydrogen to form network structures train.

at two-component systems, the reactive components become mixed just before processing. The mixtures contain one active platinum catalyst, which has the consequence that the crosslinking reaction already at room temperature and the time to processing (Pot life) is tightly limited. This results in disadvantages like one additional mixing step, an increased cleaning effort in case of technical faults and the risk of platinum contamination in containers.

Of the Need for one-component addition-crosslinking silicone rubber systems, which ideally not at room temperature and at room temperature harden as quickly as possible at elevated temperature, has been given for a long time.

There are several approaches to solve the problem of premature crosslinking at room temperature. One possibility is the use of inhibitors which are added to the mixture as additives in order to prolong the pot life. They are always used in molar excess to the catalyst component and inhibit its catalytic activity. However, as the amount of inhibitor increases, in addition to pot life extension, the reactivity of the system decreases at higher temperatures and the light-off temperature increases. There are numerous examples in the literature of inhibitors from various substance classes. In US 3,723,567 A amino-functional silanes are claimed as inhibitors. Alkyldiamines in combination with an acetylenically unsaturated alcohol are used in US 5,270,422 A used for inhibition. EP 0 761 759 A2 claims a combination of inhibitors, a phosphite is used together with another inhibitor such as maleates and ethinols. DE 19 757 221 A1 also describes the class of phosphites in the use of an inhibitor. Phosphines are in US 4,329,275 A claimed as an additive for inhibition. A combination of phosphites in conjunction with organic peroxides is used by EP 1 437 382 A1 described. In addition to negative effects on the crosslinking kinetics, the use of partially volatile inhibitors or inhibitors that release volatile constituents also proves unfavorable. Mixtures which have a complete inhibition at room temperature and the complete non-influence of the reaction rate under curing conditions by a corresponding additive, are not yet known.

Another possibility, which is fundamentally different, is to encapsulate the catalyst in a thermoplastic material which melts at elevated temperature and thereby releases the active catalyst, as in, for example, US Pat EP 0 459 464 A2 described. However, the preparation of the catalyst is relatively expensive.

A third possibility to prevent premature crosslinking of one-component systems at room temperature is the use of special platinum complexes. Platinum kinyl complexes are in US 6,252,028 B and in US 6,359,098 B described. In US 4,256,616 A Pt (0) phosphine and phosphite complexes are used in combination with tin salts and WO 03/098 890 A1 describes Pt (0) phosphite complexes containing as structural features both phosphite ligands and divinyldisiloxane ligands.

Even though the described masses significantly improved pot life at Part sufficiently high crosslinking rates in one-component formulated, addition-crosslinking materials continue to exist Need for more powerful platinum catalysts, which at elevated temperature a rapid cross-linking of the material ensure, but do not show the above-mentioned disadvantages.

task The present invention was to addition-crosslinking compositions for To provide the above-mentioned disadvantages do not show and in addition to improved dripping times also improved Enable crosslinking speed.

In the following, the term organopolysiloxanes both polymeric, oligomeric and dimeric Siloxane comprises.

• – jeweils mindestens eine Verbindung (A), (B) und (D),
• – jeweils mindestens eine Verbindung (C) und (D), und
• – jeweils mindestens eine Verbindung (A), (B), (C) und (D) wobei (A) eine organische Verbindung oder eine Siliziumorganische Verbindung, enthaltend mindestens zwei Reste mit aliphatischen Kohlenstoff-Kohlenstoff-Mehrfachbindungen, (B) ein Siliziumorganische Verbindung, enthaltend mindestens zwei Si-gebundenen Wasserstoffatome, (C) eine Siliziumorganische Verbindung, enthaltend SiC-gebundene Reste mit aliphatischen Kohlenstoff-Kohlenstoff-Mehrfachbindungen und Si-gebundene Wasserstoffatome, und (D) ein Platinkatalysator bedeuten,

dadurch gekennzeichnet, dass der Platinkatalysator (D) der allgemeinen Formel (I) entspricht, R¹ ₂Pt[P(OR² ₃)₃]₂ (I)wobei
R¹ unabhängig voneinander, gleich oder verschieden, ein

• – Halogen,
• – einfach negativer anorganischer Rest,
• – CR³ ₃ mit R³ unabhängig voneinander, gleich oder verschieden ein H, lineare oder verzweigte aliphatische Reste mit 1 bis 18 Kohlenstoffatomen, Arylalkylreste mit 6 bis 31 Kohlenstoffatomen
• – OR³ wobei R³ die oben genannte Bedeutung trägt,
• – SiR³ ₃ wobei R³ die oben genannte Bedeutung trägt,

R² unabhängig voneinander, gleich oder verschieden, ein

• – Alkyl der Formeln C_nH_2n+1 mit n = 5–18 oder C_mH_2m-1 mit m = 5–31,
• – Arylalkyl der Formel -(C₆H₅-_P)-(C_oH_2o+1)_p mit o = 1–31 und p = 1–5, wobei die Wasserstoffatome der für R¹ und R² oben genannten Verbindungen substituiert oder nicht substituiert sind durch die Gruppen -NH₂, -COOH, -F, -Br, -Cl, -Aryl oder -Alkyl

bedeuten.The subject of this application are addition-curing
Silicone compositions selected from the group containing

• In each case at least one compound (A), (B) and (D),
• - Each at least one compound (C) and (D), and
• - Each at least one compound (A), (B), (C) and (D) wherein (A) an organic compound or an organosilicon compound containing at least two radicals having aliphatic carbon-carbon multiple bonds, (B) an organosilicon compound containing at least two Si-bonded hydrogen atoms, (C) an organosilicon compound containing SiC-bonded radicals having aliphatic carbon-carbon multiple bonds and Si-bonded hydrogen atoms, and (D) a platinum catalyst,

characterized in that the platinum catalyst (D) corresponds to the general formula (I), R ¹ ₂ Pt [P (OR ² ₃ ) ₃ ] ₂ (I) in which
R ^{1 are} independently, the same or different, a

• - halogen,
• Simply negative inorganic radical,
• - CR ³ ₃ with R ^{3 are} independently, identically or differently an H, linear or branched aliphatic radicals having 1 to 18 carbon atoms, arylalkyl radicals having 6 to 31 carbon atoms
• OR ³ where R ^{3 has} the abovementioned meaning,
• - SiR ³ ₃ where R ^{3 has} the abovementioned meaning,

R ^{2 are} independently, the same or different, a

• Alkyl of the formulas C _n H _{2n + 1} with n = 5-18 or C _m H _2m-1 with m = 5-31,
• - Arylalkyl of the formula - (C ₆ H ₅ - _P ) - (C _o H _{2o + 1} ) _p with o = 1-31 and p = 1-5, wherein the hydrogen atoms substituted for R ¹ and R ² above compounds or unsubstituted by the groups -NH ₂ , -COOH, -F, -Br, -Cl, -aryl or -alkyl

mean.

It showed that the platinum catalysts (D) in particular Pt (II) -phosphitkomplexe with platinum in the oxidation state + II as central metal and phosphorus in the oxidation state + III to the improved properties of lead silicone compositions according to the invention.

at It may be in the compositions of the invention One-component silicone compositions as well as two-component silicone compositions act. In the latter case, the two components the compositions of the invention all components contained in any combination, generally with the proviso that one component does not simultaneously contain siloxanes with aliphatic Multiple bond, siloxanes with Si-bonded hydrogen and catalyst, so essentially not at the same time the components (A), (B) and (D) and (C) and (D), respectively. Preferably it is the compositions of the invention however, one-component compositions.

The used in the compositions of the invention Compounds (A) and (B) or (C) are known chosen so that networking is possible. For example, compound (A) has at least two aliphatic groups unsaturated radicals on and (B) at least three Si-bonded Hydrogen atoms, or compound (A) has at least three aliphatic unsaturated radicals and siloxane (B) at least two Si-bonded hydrogen atoms, or instead of compound (A) and (B) siloxane (C) is used, which is aliphatically unsaturated Radicals and Si-bonded hydrogen atoms in the abovementioned ratios having. Also, mixtures of (A) and (B) and (C) are those with the above mentioned ratios of aliphatically unsaturated Radicals and Si-bonded hydrogen atoms.

at the compound (A) used according to the invention it may be preferably silicon-free organic compounds at least two aliphatically unsaturated groups as well to organosilicon compounds having preferably at least two aliphatic unsaturated groups or their mixtures.

Examples for silicon-free organic compounds (A), 1,3,5-trivinylcyclohexane, 2,3-dimethyl-1,3-butadiene, 7-methyl-3-methylene-1,6-octadiene, 2-methyl-1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 4,7-methylene-4,7,8,9-tetrahydroindene, Methylcyclopentadiene, 5-vinyl-2-norbornene, bicyclo [2.2.1] hepta-2,5-diene, 1,3-diisoproppenylbenzene, vinyl group-containing polybutadiene, 1,4-divinylcyclohexane, 1,3,5-triallylbenzene, 1,3,5-trivinylbenzene, 1,2,4-trivinylcyclohexane, 1,3,5-triisopropenylbenzene, 1,4-divinylbenzene, 3-methylheptadiene (1,5), 3-phenyl-hexadiene- (1,5), 3-vinyl-hexadiene (1,5 and 4,5-dimethyl-4,5-diethyl-octadiene- (1,7), N, N'-methylene bis-acrylic acid amide, 1,1,1-tris (hydroxymethyl) propane triacrylate, 1,1,1-tris (hydroxymethyl) propane trimethacrylate, Tripropylene glycol diacrylate, diallyl ether, diallylamine, diallyl carbonate, N, N'-diallylurea, triallylamine, tris (2-methylallyl) amine, 2,4,6-triallyloxy-1,3,5-triazine, Triallyl-s-triazine-2,4,6 (1H, 3H, 5H) -trione, diallylmalonic acid ester, Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, poly (propylene glycol) methacrylate.

Preferably contain the silicone compositions according to the invention as constituent (A) at least one aliphatically unsaturated Organosilicon compound, all of which hitherto in addition-crosslinking compositions used, aliphatically unsaturated organosilicon compounds can be used, such as silicone block copolymers with urea segments, silicone block copolymers with amide segments and / or imide segments and / or ester amide segments and / or polystyrene segments and / or silarylene segments and / or carborane segments and silicone graft copolymers with ether groups.

As organosilicon compounds (A) which have SiC-bonded radicals with aliphatic carbon-carbon multiple bonds, it is preferable to use linear or branched organopolysiloxanes of units of the general formula (II) R _a R ⁴ _b SiO _{(4-ab) / 2} (II) used, where
R independently, the same or different, an organic or inorganic radical free of aliphatic carbon-carbon multiple bonds,
R ^{4 are} independently, identically or differently a monovalent, substituted or unsubstituted, SiC-bonded hydrocarbon radical having at least one aliphatic carbon-carbon multiple bond,
a is 0, 1, 2 or 3, and
b is 0, 1 or 2
mean,
with the proviso that the sum a + b is less than or equal to 3 and at least 2 radicals R ⁴ are present per molecule.

at Radicals R may be monovalent or polyvalent radicals, where the polyvalent radicals, such as bivalent, trivalent and tetravalent residues, then several, such as two, three or four, Connect siloxy units of the formula (II) together.

Further examples of R are the monovalent radicals -F, -Cl, -Br, OR ⁵ , -CN, -SCN, -NCO and SiC-bonded, substituted or unsubstituted hydrocarbon radicals which are bonded to oxygen atoms or the group -C (O) - may be interrupted, as well as divalent, on both sides according to formula (II) Si-bonded radicals. If radical R is SiC-bonded, substituted hydrocarbon radicals, preferred substituents are halogen atoms, phosphorus-containing radicals, cyano radicals, -OR ⁵ , -NR ⁵ -, -NR ⁵ ₂ , -NR ⁵ -C (O) -NR ⁵ ₂ , -C (O) -NR ⁵ ₂ , -C (O) R ⁵ , -C (O) OR ⁵ , -SO ₂ -Ph and -C ₆ F ₅ . Here, R ^5, independently of one another, denote, identically or differently, a hydrogen atom or a monovalent hydrocarbon radical having 1 to 20 carbon atoms and Ph is phenyl.

Examples R radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-bulyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as Cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical, Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

Examples of substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2`, 2`-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, haloaryl radicals, such as the o-, m- and p-chlorophenyl radical, - (CH ₂ ) -N (R ⁵ ) C (O) NR ⁵ ₂ , - (CH ₂ ) _n -C (O) NR ⁵ ₂ , - (CH ₂ ) _n -C ( O) R ⁵ , - (CH ₂ ) _n -C (O) OR ⁵ , - (CH ₂ ) _n -C (O) NR ⁵ ₂ , - (CH ₂ ) -C (O) - (CH ₂ ) _m C (O) CH _3, - (CH ₂₎ -O-CO-R ^5, - (CH ₂₎ - NR ⁵ - (CH _{2) m} -NR ⁵ _2, - (CH _{2) n} -O- (CH ₂ ) _m CH (OH) CH ₂ OH, (CH ₂ ) _n (OCH ₂ CH ₂ ) _m OR ⁵ , - (CH ₂ ) _n -SO ₂ -Ph and - (CH ₂ ) _n -OC ₆ F ₅ , where R ⁵ and Ph correspond to the meaning given above and n and m denote identical or different integers between 0 and 10.

Examples of R equal to divalent radicals which are Si-bonded on both sides according to formula (II) are those which derive from the monovalent examples mentioned above for radical R in that additional bonding takes place by substitution of a hydrogen atom; examples of such radicals are - ( CH ₂ ) -, -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, -CH (CH ₃ ) -CH ₂ -, -C ₆ H ₄ -, -CH (Ph) -CH ₂ -, -C (CF ₃ ) ₂ -, - (CH ₂ ) _n -C ₆ H ₄ - (CH ₂ ) _n -, - (CR ₂ ) _n -C ₆ H ₄ -C ₆ H ₄ - (CH ₂ ) _n -, - (CH ₂ O) _m , (CH ₂ CH ₂ O) _m , - (CH ₂ ) _n -O _x -C ₆ H ₄ -SO ₂ -C ₆ H ₄ -O _x - (CH ₂ ) _n -, wherein x is 0 or 1, and Ph, m and n have the meaning given above.

Prefers R is a monohydric, aliphatic radical Carbon-carbon multiple bonds free, SiC-bonded, optionally substituted hydrocarbon radical having 1 to 18 Carbon atoms, more preferably a monovalent, of aliphatic carbon-carbon multiple bonds free, SiC-bonded hydrocarbon radical having 1 to 6 carbon atoms, in particular the methyl or phenyl radical.

The radical R ⁴ can be any groups which are accessible to an addition reaction (hydrosilylation) with an SiH-functional compound. If radical R ⁴ is SiC-bonded, substituted hydrocarbon radicals, preferred substituents are halogen atoms, cyano radicals and -OR ⁵ , where R ^{5 has} the abovementioned meaning.

Radical R ⁴ is preferably alkenyl and alkynyl groups having 2 to 16 carbon atoms, such as vinyl, allyl, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl Cyclopentadienyl, cyclohexenyl, vinylcyclohexylethyl, divinylcyclohexylethyl, norbornenyl, vinylphenyl and styryl radicals, vinyl, allyl and hexenyl radicals being particularly preferably used.

The molecular weight of component (A) can vary within wide limits, for example between 10 ² and 10 ⁶ g / mol. For example, constituent (A) may be a relatively low molecular weight alkenyl-functional oligosiloxane, such as 1,2-divinyltetramethyldisiloxane, but may also be a high polymer polydimethylsiloxane having chain or terminal Si-bonded vinyl groups, e.g. B. with a molecular weight of 10 ⁵ g / mol (determined by NMR number average). Also, the structure of the component (A) forming molecules is not specified; In particular, the structure of a relatively high molecular weight, that is to say oligomeric or polymeric siloxane, can be linear, cyclic, branched or even resinous, network-like. Linear and cyclic polysiloxanes are preferably composed of units of the formula R ₃ SiO _1/2 , R ⁴ R ₂ SiO _1/2 , R ⁴ RSiO _1/2 and R ₂ SiO _2/2 , where R and R ⁴ are as defined above to have. Branched and network-like polysiloxanes additionally contain trifunctional and / or tetrafunctional units, preference being given to those of the formulas RSiO _3/2 , R ⁴ SiO _3/2 and SiO _4/2 . Of course, mixtures of different, the criteria of the component (A) sufficient siloxanes can be used.

Especially preferably as component (A) the use is vinyl-functional, essentially linear polydiorganosiloxanes having a viscosity from 0.01 to 500,000 Pa · s, more preferably from 0.1 up to 100,000 Pa · s, each at 25 ° C.

When Organosilicon compound (B) can all be hydrogen functional Organosilicon compounds are used, which also previously in addition-crosslinkable compositions have been used.

As organopolysiloxanes (B) which have Si-bonded hydrogen atoms, it is preferable to use linear, cyclic or branched organopolysiloxanes of units of the general formula (III) R _c H _d SiO _{(4-cd) / 2} (III) used, where
R has the meaning given above,
c is 0.1 2 or 3 and
d is 0, 1 or 2,
with the proviso that the sum of c + d is less than or equal to 3 and there are at least two Si-bonded hydrogen atoms per molecule.

Preferably contains the inventively used Organopolysiloxane (B) Si-bonded hydrogen in the range of 0.04 to 1.7 weight percent, based on the total weight of the organopolysiloxane (B).

The molecular weight of component (B) may also vary within wide limits, such as between 10 ² and 10 ⁶ g / mol. For example, constituent (B) may be, for example, a relatively low molecular weight SiH-functional oligosiloxane, such as tetramethyldisiloxane, but also a high-polymer polydimethylsiloxane having SiH groups via a chain or terminal or a silicone resin having SiH groups.

Also, the structure of the component (B) forming molecules is not fixed; In particular, the structure of a relatively high molecular weight, that is to say oligomeric or polymeric SiH-containing siloxane can be linear, cyclic, branched or even resinous, network-like. Linear and cyclic polysiloxanes (B) are preferably composed of units of the formula R ₃ SiO _1/2 , HR ₂ SiO _1/2 , HRSiO _2/2 and R ₂ SiO _2/2 , wherein R has the meaning given above. Branched and network-like polysiloxanes additionally contain trifunctional and / or tetrafunctional units, preference being given to those of the formulas RSiO _3/2 , HSiO _3/2 and SiO _4/2 , where R has the meaning given above.

Of course can also mix different, the criteria of the component (B) of sufficient siloxanes are used. In particular, the molecules forming component (B) can be used in addition to the obligatory SiH groups possibly also at the same time contain aliphatically unsaturated groups. Especially preferred is the use of low molecular weight SiH-functional compounds such as tetrakis (dimethylsiloxy) silane and tetramethylcyclotetrasiloxane, and higher molecular weight, SiH-containing siloxanes, such as poly (hydrogenmethyl) siloxane and poly (dimethylhydrogenmethyl) siloxane having a viscosity at 25 ° C from 10 to 10,000 mPa · s, or analogous SiH-containing compounds in which a part of the methyl groups 3,3,3-trifluoropropyl or phenyl groups is replaced.

component (B) is preferably in such an amount in the invention crosslinkable silicone compositions that contain the molar ratio from SiH groups to aliphatically unsaturated groups (A) is 0.1 to 20, more preferably between 1.0 and 5.0. The components used according to the invention (A) and (B) are commercial products or in chemistry can be produced by conventional methods.

Instead of of component (A) and (B), the inventive Silicone Compositions Organopolysiloxanes (C) which Simultaneously aliphatic carbon-carbon multiple bonds and Si-bonded ones Have hydrogen atoms included. Also, the Silicone compositions according to the invention all contain three components (A), (B) and (C).

If siloxanes (C) are used, these are preferably those of units of the general formulas (IV), (V) and (VI) R _f SiO _4/2 (IV) R _g R ⁴ SiO _{3-g / 2} (V) R _h HSiO _{3-h / 2} (VI) in which
R and R ^{4 have} the meaning given above
f is 0, 1, 2 or 3,
g is 0, 1 or 2 and
h is 0, 1 or 2,
with the proviso that at least 2 radicals R ⁴ and at least 2 Si-bonded hydrogen atoms are present per molecule.

Examples of organopolysiloxanes (C) are those of SO _4/2 , R ₃ SiO _1/2 -, R ₂ R ⁴ SiO _1/2 - and R ₂ HSiO _1/2 - units, so-called MP resins, these resins additionally RSiO _3/2 - and may contain R ₂ SiO units, and linear organopolysiloxanes consisting essentially of R ₂ R ⁴ SiO _1/2 , R ₂ SiO and RHSiO units with R and R ^{11 have} the abovementioned meaning.

The Organopolysiloxanes (C) preferably have an average Viscosity from 0.01 to 500,000 pass, more preferred 0.1 to 100,000 Pa · s each at 25 ° C. organopolysiloxanes (C) can be prepared by methods commonly used in chemistry.

• – jeweils mindestens eine Verbindung (A), (B) und (D),
• – jeweils mindestens eine Verbindung (C) und (D), und
• – jeweils mindestens eine Verbindung (A), (B), (C) und (D) wobei (A) eine organische Verbindung oder eine Siliziumorganische Verbindung, enthaltend mindestens zwei Reste mit aliphatischen Kohlenstoff-Kohlenstoff-Mehrfachbindungen, (B) ein Siliziumorganische Verbindung, enthaltend mindestens zwei Si-gebundenen Wasserstoffatome, (C) eine Siliziumorganische Verbindung, enthaltend SiC-gebundene Reste mit aliphatischen Kohlenstoff-Kohlenstoff-Mehrfachbindungen und Si- gebundene Wasserstoffatome, und (D) ein Platinkatalysator bedeuten,

wobei der Platinkatalysator (D) der folgenden Definition entspricht.Addition-crosslinking silicone compositions according to the invention are selected from the group comprising

• In each case at least one compound (A), (B) and (D),
• - Each at least one compound (C) and (D), and
• - Each at least one compound (A), (B), (C) and (D) wherein (A) an organic compound or an organosilicon compound containing at least two radicals having aliphatic carbon-carbon multiple bonds, (B) an organosilicon compound containing at least two Si-bonded hydrogen atoms, (C) an organosilicon compound containing SiC-bonded radicals having aliphatic carbon-carbon multiple bonds and Si-bonded hydrogen atoms, and (D) a platinum catalyst,

wherein the platinum catalyst (D) corresponds to the following definition.

One Another object of the invention is the component (D), since they crucial for the properties of the invention Silicone compositions is.

• – Halogen,
• – einfach negativer anorganischer Rest,
• – CR³ ₃ mit R³ unabhängig voneinander, gleich oder verschieden ein H, lineare oder verzweigte aliphatische Reste mit 1 bis 18 Kohlenstoffatomen, Arylalkylreste mit 6 bis 31 Kohlenstoffatomen
• – OR³ wobei R³ die oben genannte Bedeutung trägt,
• – SiR³ ₃ wobei R³ die oben genannte Bedeutung trägt,

R² unabhängig voneinander, gleich oder verschieden, ein

• – Alkyl der Formeln C_nH_2n+1 mit n = 5–18 oder C_mH_2m-1 mit m = 5–31,
• – Arylalkyl der Formel -(C₆H_5-p)-(COH_2o+1)_p mit o = 1–31 und p = 1–5,

wobei die Wasserstoffatome der für R¹ und R² oben genannten Verbindungen substituiert oder nicht substituiert sind durch die Gruppen -NH₂, -COOH, -F, -Br, -Cl, -Aryl oder -Alkyl
bedeuten.The platinum catalyst (D) according to the invention corresponds to the general formula (I), R ¹ ₂ Pt [P (OR ² ₃ ) ₃ ] ₂ (I) in which
R ^{1 are} independently, the same or different, a

• - halogen,
• Simply negative inorganic radical,
• - CR ³ ₃ with R ^{3 are} independently, identically or differently an H, linear or branched aliphatic radicals having 1 to 18 carbon atoms, arylalkyl radicals having 6 to 31 carbon atoms
• OR ³ where R ^{3 has} the abovementioned meaning,
• - SiR ³ ₃ where R ^{3 has} the abovementioned meaning,

R ^{2 are} independently, the same or different, a

• Alkyl of the formulas C _n H _{2n + 1} with n = 5-18 or C _m H _2m-1 with m = 5-31,
• - arylalkyl of the formula - (C ₆ H _5-p ) - (COH _{2o + 1} ) _p with o = 1-31 and p = 1-5,

wherein the hydrogen atoms of the compounds mentioned above for R ¹ and R ² are substituted or unsubstituted by the groups -NH ₂ , -COOH, -F, -Br, -Cl, -aryl or -alkyl
mean.

(D) represents a specially prepared platinum complex compound. The preparation process is carried out by the reaction of a platinum salt such as K ₂ PtCl ₄ , Na ₂ PtCl ₄ , PtCl ₂ , PtBr ₂ or PtI ₂ , with the respective phosphite of the formula [-P (OR ² ₃ ) ₃ ], wherein R ^{2 has} the abovementioned meaning, in a suitable solvent for the reaction at a temperature of 0 to 110 ° C. The preparation of the phosphites used for this reaction corresponds to common methods of the prior art or they are commercially available.

Before mixing into the silicone composition according to the invention, the compound (D) is isolated and its purity is checked by conventional methods. The phosphite of the formula [-P (OR ² ₃ ) ₃ ] used coordinates to the central metal, where R ^{2 has} the abovementioned meaning.

The following is an exemplary listing of platinum-phosphite complexes [D] according to the invention in which R ¹ = Cl, R ^{2 was} varied and which is synthesized in the way described above.
PtCl ₂ [P (-O-2-methylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-ethylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-propylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-isopropylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-sec-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-tert-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-pentylphenyl) ₃ ] ₂ ,
PtCl ₂ {P (-O-2- (1-methylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2-hexylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-heptylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-octylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-nonylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-decylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-octadecylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2-octadecenylphenyl) ₃ ] ₂ ,
PtCl ₂ {P (-O-2- (1,1-dimethylpropyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P (-O-2- (1,1-dimethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P (-O-2- (1,1-dimethylpentyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P (-O-2- (1,1-dimethylhexyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2- (1,1-dimethylheptyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2- (1,1,3,3-tetramethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-4-methylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-ethylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-propylphenyl)) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-isopropylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-sec-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-tert-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-pentylphenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-4- (1-methylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-4-hexylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-heptylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-ctylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-nonylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-decylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-octadecylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-4-octadecenylphenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-4- (1,1-dimethylpropyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-4- (1,1-dimethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P (-O-4- (1,1-dimethylpentyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-4- (1,1-dimethylhexyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-4- (1,1-dimethylheptyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-4- (1,1,3,3-tetramethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,4-dimethylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-diethylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-dipropylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-diisopropylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-dibutylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-di-sec-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-di-tert-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-di-pentylphenyl) ₃ ] ₂ ,
PtCl ₂ {P (-O-2,4-bis (1-methylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,4-dihexylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-diheptylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-dioctylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-dinonylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-didecylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-dioctadecylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,4-dioctadecenylphenyl) ₃ ] ₂ ,
PtCl ₂ {P (-O-2,4-bis (1,1-dimethylpropyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,4-bis (1,1-dimethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,4-bis (1,1-dimethylpentyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [4-bis (1,1-dimethylhexyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,4-bis (1,1-dimethylheptyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,4-bis (1,1,3,3-tetramethylbutyl) phenyl] ₃ } ₂
PtCl ₂ [P (-O-2,5-dimethylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diethylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dipropylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diisopropylphenyl)) ₃ ] ₂
PtCl ₂ [P (-O-2,5-dibutylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-sec-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-tert-butylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-pentylphenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-2,5-bis (1-methylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,5-dihexylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diheptylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dinonylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-didecylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctadecylphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctadecenylphenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylpropyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylpentyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylhexyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylheptyl) phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1,3,3-tetramethylbutyl) phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,5-dimethyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diethyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dipropyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diisopropyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dibutyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-sec-butyl-4-methoxyphenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-tert-butyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-pentyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-2,5-bis (1-methylbutyl) -4-methoxy-phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,5-dihexyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diheptyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dinonyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-didecyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctadecyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctadecenyl-4-methoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylpropyl) -4-methoxyphenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylbutyl) -4-methoxyphenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylpentyl) -4-methoxyphenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylhexyl) -4-methoxyphenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylheptyl) -4-methoxyphenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1,3,3-tetramethylbutyl) -4-methoxyphenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,5-dimethyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diethyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dipropyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diisopropyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dibutyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-sec-butyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-tert-butyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-di-pentyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-2,5-bis (1-methylbutyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ [P (-O-2,5-dihexyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-diheptyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dinonyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-didecyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctadecyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ [P (-O-2,5-dioctadecenyl-4-ethoxy-phenyl) ₃ ] ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylpropyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylbutyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylpentyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylhexyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1-dimethylheptyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ {P [-O-2,5-bis (1,1,3,3-tetramethylbutyl) -4-ethoxy-phenyl] ₃ } ₂ ,
PtCl ₂ {P [(- O-2-tert-butyl-5-methylphenyl) (- O-2,4-di-tert-butylphenyl) ₂ ]} ₂ ,
PtCl ₂ {P [(- O-2,4-di-tert-pentylphenyl) (- O-2,4-di-tert-butylphenyl) ₂ ]} ₂ ,
PtCl ₂ {P [(- O-2-tert-butylphenyl) (- O-2,4-di-tert-butylphenyl) ₂ ]} ₂ ,

Enclosed is an exemplary list of inventive platinum-phosphite complexes [D] in which R ¹ = was varied, R ^{2 is} generally a phosphite compound (= phosphite) and which are also synthesized in the manner described above.
PtF ₂ (phosphite) ₂ ,
PtBr ₂ (phosphite) ₂ ,
PtI ₂ (phosphite) ₂ ,
Pt (CH ₃ ) ₂ (phosphite) ₂ ,
Pt (CH ₂ CH ₃ ) ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₂ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₃ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₄ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₅ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₆ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₇ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [(CH ₂ ) ₁₇ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [C (CH ₃ ) ₂ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [C (CH ₃ ) ₂ CH ₂ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [C (CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [C (CH ₃ ) ₂ (CH ₂ ) ₃ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [C (CH ₃ ) ₂ (CH ₂ ) ₄ CH ₃ ] ₂ (phosphite) ₂ ,
Pt (OCH ₃ ) ₂ (phosphite) ₂ ,
Pt (OCH ₂ CH ₃ ) ₂ (phosphite) ₂ ,
Pt [O (CH ₂ ) ₂ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [O (CH ₂ ) ₃ CH ₃ ] ₂ (phosphite) ₂ ,
Pt [Si (CH ₃ ) ₃ ] ₂ (phosphite) ₂ ,

The platinum catalysts (D) according to the invention are not limited to the abovementioned examples, since a multiplicity of substituents can be used for R ¹ . The radicals R ¹ can independently be monovalent radicals which are capable of forming an uncharged complex from the central metal platinum in the oxidation state + II, which carries two phosphite ligands, in sum.

Examples of R ¹ as a uninegative inorganic residues, pseudohalides are selected from the group consisting of N3 ^-, CN ^-, OCN ^-, CNO ^-, SCN ^-, NCS ^-, SeCN ^-.

Preferred radicals R ^{1 are} halogens, pseudohalogens and alkyl radicals.

Examples of R ¹ are, in addition to the -Cl, also -F, -Br, -I, -CN, -N3, -OCN, -NCO, -CNO, -SCN, -NCS, -SeCN, -CH ₃ , -CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , -C ₆ H ₅ , -CH ₂ (Ph) -CH ₃ , C _v H _{2v + 1} , C _v H _2v-1 , - (C ₆ H _5-W ) - (C _v H _{2v + 1} ) _w with v = 1-18 and w = 1-5, -O-alkyl, -O-aryl, -O-aryl-alkyl, - Si (alkyl) ₃ , -Si (aryl) ₃ , -Si (aryl-alkyl) ₃ . Particularly preferred for R ¹ are halogens and linear or branched aliphatic radicals having 1 to 18 carbon atoms, optionally, the H atoms contained therein by groups such as -NH ₂ , -COOH, F, Br, Cl, alkyl, aryl or - Arylalkyl replaced.

Preferred radicals R ^{2 are} alkyl radicals.

Examples of R ² are n-pentyl, isopentyl, neo-pentyl, tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-naphthyl radical. Octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical.

Also preferred for R ^{2 are} _{arylalkyl radicals} - (C ₆ H ₅ - _P ) - (C _o H _{2o + 1} ) _p where o is between 1-18 and p is between 1-5, more preferably o is between 1-18 and p between 2-3. In a further embodiment particularly preferred for R ² , at least one alkyl substituent is attached at the 2-position of the phenyl ring in the arylalkyl radical. Compared with unsubstituted arylalkyl phosphites, platinum complex compounds having substituted phosphites have the advantage of a significantly lower light-off temperature.

The Platinum catalysts according to the invention (D) are useful as catalysts for the well-known hydrosilylation reaction in organosilicon chemistry, as a catalyst for the hydrogenation of unsaturated organic compounds or polymers and for oligomerization of acetylene and other alkynes.

The Platinum catalysts according to the invention (D) have furthermore the advantage that terminal double bonds do not rearrange in the hydrosilylation, resulting in weakly reactive remained isomerized starting product.

The platinum catalysts according to the invention also have the advantage that no platinum colloids are formed and by Their use does not result in discoloration.

Next the above-mentioned components (A), (B), (C) and (D) still further components (E), (F) or (G) in the inventive Be included silicone compositions.

Components (E), such as, for example, inhibitors and stabilizers, serve for the targeted adjustment of the processing time, light-off temperature and crosslinking rate of the silicone compositions according to the invention. These inhibitors and stabilizers are well known in the field of addition-crosslinking compositions. Examples of common inhibitors are acetylenic alcohols, such as 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecyne-3 ol, polymethylvinylcyclosiloxanes such as 1,3,5,7-tetravinyltetramethyltetracyclosiloxane low molecular weight silicone oils with methylvinyl-SiO _1/2 groups and / or R ₂ vinyl SiO _{1/2 end} groups. such as divinyltetramethydisiloxane tetravinyldimethyldisiloxane, trialkylcyanurates, alkyl maleates such as diallyl maleates, dimethyl maleate and diethyl maleate, alkylfumarates such as diallyl fumarate and diethylfurnarate, organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and pinane hydroperoxide, organic peroxides, organic sulfoxides, organic amines. Diamines and amides, phosphanes and phosphites, nitriles, triazoles, diaziridines and oximes. The effect of these inhibitor additives (E) depends on their chemical structure, so that the concentration must be determined individually. Inhibitors and inhibitor mixtures are preferably added in a proportion of 0.00001% to 5% based on the total weight of the mixture, preferably 0.00005 to 2% and more preferably 0.0001 to 1%.

Components (F) are all other additives substances that were previously used for the production of addition-crosslinkable compositions. Examples of reinforcing fillers which can be used as component (F) in the silicone compositions according to the invention are fumed or precipitated silicas having BET surface areas of at least 50 m ² / g and carbon blacks and activated carbons such as furnace carbon black and acetylene black, where pyrogenic and precipitated silicas having BET surface areas of at least 50 m ² / g are preferred. The silicic acid fillers mentioned can have a hydrophilic character or be hydrophobized by known processes. When incorporating hydrophilic fillers, it is necessary to add a hydrophobing agent. The content of the crosslinkable composition of active reinforcing filler (F) of the present invention is in the range of 0 to 70% by weight, preferably 0 to 50% by weight.

The silicone composition of the present invention may optionally contain the component (F) as further additives in an amount of up to 70% by weight, preferably 0.0001 to 40% by weight. These additives can z. Inactive fillers, resinous polyorganosiloxanes other than siloxanes (A), (B) and (C), reinforcing and non-reinforcing fillers, fungicides, perfumes, rheological additives, corrosion inhibitors, antioxidants, light stabilizers, flame retardants and agents be to influence the electrical properties dispersing aids, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers, etc. These include additives such as quartz powder, diatomaceous earth, clays, chalk, lithopones, carbon blacks, graphite, metal oxides, metal carbonates, sulfates, metal salts of carboxylic acids, metal dusts, fibers such as glass fibers, plastic fibers, plastic powder, Me tall dusts, dyes, pigments, etc.

The silicone composition according to the invention can optionally as further component (G) at least one further addition-crosslinking Contain catalysts that corresponds to the prior art, for example Hydrosilylation catalysts or peroxides.

Examples for such catalysts (G) are metallic and finely divided Platinum based on supports such as silica, alumina or activated carbon, compounds or complexes of platinum, such as Platinum halides, e.g. PtCl4, H2PtCl6 .6H20, Na2PtCl4 .4H20, Platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, Platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H2PtCl6 · 6H20 and cyclohexanone, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetra-methyldisiloxane complexes with or without detectable inorganic halogen content, Bis (gamma-picoline) platinum dichloride, trimethylenedipyridine platinum dichloride, Dicyclopentadiene platinum dichloride, dimethylsulfoxydethylenepiatine (II) di-chloride, Cyclooctadiene-platinum dichloride, norbornadiene-platinum dichloride, gamma-picoline-platinum dichloride, Cyclopentadiene platinum dichloride, as well as reaction products of platinum tetrachloride with olefin and primary amine or secondary amine or primary and secondary amine, such as the reaction product from in 1-octene dissolved platinum tetrachloride with sec-butylamine or ammonium-platinum complexes.

Further Examples of such a catalyst (G) are organic Peroxides such as acyl peroxides such as dibenzoyl peroxide, bis (4-chlorobenzoyl) peroxide, Bis (2,4-dichlorobenzoyl) peroxide and bis (4-methylbenzoyl) peroxide; Alkyl peroxides and aryl peroxides such as di-tert-butyl peroxide, 2,5-bis (tert-butylperoxy) -2,5-dimethylhexane, dicumyl peroxide and 1,3-bis (tert-butylperoxy-isopropyl) benzene; Perketale, like 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane; peresters, such as diacetyl peroxydicarbonate, tert-butyl perbenzoate, tert-butyl peroxy-isopropyl carbonate, Tert-butyl peroxy isononanoate, dicyclohexyl peroxydicarbonate and 2,5-dimethyl-2,5-diperbenzoat.

The Silicone compositions according to the invention can, if necessary, dissolved in liquids, dispersed be suspended or emulsified The inventive Compositions can - in particular depending on Viscosity of ingredients and filler content - low viscosity and be pourable, have a pasty consistency be powdery or supple, highly viscous masses as is known in the art commonly referred to as RTV-1, RTV-2, LSR and HTV compositions the case may be. In particular, the inventive Compositions, if they are highly viscous, in the form of granules be prepared. Here, the individual granules all Contain components, or inventively used Components are incorporated separately in different granules. With regard to the elastomeric properties of the crosslinked invention Silicone compositions also encompass the full spectrum, starting with extremely soft silicone gels, over rubbery ones Materials up to highly cross-linked silicones with vitreous Behavior.

The Preparation of the silicone compositions according to the invention can be done by known methods, such as by uniform mixing of the individual components. The order is arbitrary, but preferred is the uniform Mixing of the platinum catalyst (D) and optionally (G) with a mixture of (A), (B) optionally (E) and (F). The inventively used Platinum catalyst (D) and optionally (G) can be used as solid substance or as a solution - in a suitable solvent dissolved - or as a so-called batch - evenly with a small amount (A) or (A) mixed with (E) - incorporated become.

at the components (A) used according to the invention (G) can each be a single type of such Component, as well as a mixture of at least two different Types of such a component act. The invention by attaching Si-bonded hydrogen to an aliphatic multiple bond Crosslinkable silicone compositions can be found in the the same conditions are crosslinked, as the previously known by Hydrosilylation reaction crosslinkable compositions.

Preferably these are temperatures of 100 to 220 ° C, more preferably from 130 to 190 ° C, and a pressure from 900 to 1100 hPa. But it can also be higher or lower temperatures and pressures are used.

Another object of the present invention are molded articles produced by crosslinking the compositions of the invention.

The Silicone compositions of the invention as well as the crosslinking products prepared therefrom can be used for all purposes, for the so far crosslinkable to elastomer organopolysiloxane compositions or elastomers were used. This includes, for example, the Silicone coating or impregnation of any substrates, the production of molded parts, for example by injection molding, Vacuum extrusion process, extrusion molding molding, and impressions, the use as sealing embedding and potting compounds, etc.

The Crosslinkable silicone compositions according to the invention have the advantage of using them in a simple process easily accessible starting materials and thus economically can be produced. The invention crosslinkable compositions have the further advantage that as a one-component formulation at 25 ° C and ambient pressure have a good storage stability and only at elevated Quickly network temperature. The invention Silicone compositions have the advantage that they are two-component Formulation after mixing the two components a crosslinkable Siliconmasse give their processability over a long term at 25 ° C and ambient pressure remains, so show extremely long pot life, and only at elevated temperature quickly networked.

at the production of the crosslinkable invention Compositions, it is of great advantage that the platinum catalyst (D) dose well and easy to incorporate.

The Compositions according to the invention have the Furthermore, the advantage that the resulting crosslinked silicone rubbers have an excellent transparency.

The Compositions of the invention also have the advantage that the hydrosilylation reaction does not interfere with the Reaction time slows down.

Examples

In the examples below describe all information parts and percentages unless otherwise stated on the weight. Unless otherwise stated, the following are Examples at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie at about 20 ° C, or at a temperature that occurs when the reactants are combined at room temperature without additional heating or cooling adjusts. In the following all relate Viscosity data to a temperature of 25 ° C.

Preparation of the catalyst 1

A suspension of 2.08 g K ₂ PtCl ₄ in 40 ml abs. Ethanol and a solution of 4.79 g of tris (2-tert-butylphenyl) phosphite in 20 ml of abs. Ethanol was combined under nitrogen and heated to boiling for one hour. The solvent was removed and the residue taken up in 40 ml of diethyl ether. It was extracted three times with 20 ml of water each time. The organic phase is dried over magnesium sulfate, filtered through a fluted filter and stripped off. 5.50 g of a platinum complex of the following formula were isolated: PtCl ₂ [P (-O-2-tert-butylphenyl) ₃ ] ₂ ,

Preparation of the catalyst 2

A suspension of 2.08 g of K ₂ PtCl ₄ in 40 ml of water 6.89 g of tris (4-nonylphenyl) phosphite were combined under nitrogen and heated to boiling for one hour. The product is obtained as a white solid. After filtration, it is washed with EtOH. 6.95 g of a platinum complex of the following formula were isolated: PtCl ₂ [P (-O-4-nonylphenyl) ₃ ] ₂

Preparation of the catalyst 3

A suspension of 1.33 g of PtCl ₂ in 40 ml of dichloromethane and a solution of 9.05 g of tris- (1,1-dime butylbutyl-4-methoxyphenyl) phosphite in 20 ml of dichloromethane was combined under nitrogen and heated to boiling for one hour. After removal of the solvent, the residue is taken up in diethyl ether and dried with magnesium sulfate. After filtration through a glass frit, the filtrate is concentrated. There was isolated 7.54 g of a platinum complex of the formula below: PtCl ₂ {P [-O-2,5-bis (1,1-dimethylbutyl-4-methoxy-phenyl)] ₃ } ₂

Preparation of the catalyst 4

A suspension of 1.33 g of PtCl ₂ in 40 ml of acetonitrile and a solution of 6.05 g of bis (2,4-di-tert-butylphenyl) - (2-tert-butyl-5-methylphenyl) phosphite in 20 Acetonitrile was combined under nitrogen and heated to boiling for one hour. During this process, the product oils out. The solvent is stripped off, the oily residue is taken up in 30 ml of diethyl ether, dried over sodium sulfate. After filtration, the solvent is removed. 5.95 g of a platinum complex of the following formula were isolated: PtCl ₂ [P (-O-2,4-di-tert-butylphenyl) ₂ ) - (- O-2-tert-butyl-5-methylphenyl)] ₂

Preparation of the catalyst 5

A suspension of 1.33 g of PtCl ₂ in 40 ml of acetonitrile and a solution of 6.47 g of tris (2,4-di-tert-butylphenyl) phosphite in 20 ml of acetonitrile were combined under nitrogen and boiled for one hour heated. The product fails. The suspension is cooled to -20 ° C. After filtration through a glass filter, the product is dried. 5.83 g of a platinum complex of the formula below were isolated: PtCl ₂ [P (-O-2,4-di-tert-butylphenyl) ₃ ] ₂

Preparation of the catalyst 6

A suspension of 2.08 g K ₂ PtCl ₄ in 40 ml abs. Ethanol and a solution of 7.31 g of tris- (isodecyl) phosphite in 20 ml abs. Ethanol was combined under nitrogen and heated to boiling for one hour. The solvent was removed and the residue taken up in 40 ml of diethyl ether. It was extracted three times with 20 ml of water each time. The organic phase is dried over magnesium sulfate, filtered through a fluted filter and stripped off. 7.15 g of a platinum complex of the formula below were isolated: PtCl ₂ [P (-O-isodecyl) ₃ ] ₂

Preparation of the catalyst 7

A suspension of 1.33 g of PtCl ₂ in 40 ml of acetonitrile and a solution of 5.63 g of tris (2-tert-butyl-4-ethyl) phosphite in 20 ml of acetonitrile were combined under nitrogen and heated to boiling for one hour. The product fails. The suspension is cooled to -20 ° C. After filtration through a glass filter, the product is dried. 5.83 g of a platinum complex of the formula below were isolated: PtCl ₂ [P (-O-2-tert-butyl-4-ethylphenyl) ₃ ] ₂

Preparation of the catalyst 8

To 2.0 g of a suspension of catalyst 2 in 30 ml of abs. Diethyl ether are added at -20 ° C 5 ml of a 1.0 molar solution of trimethylaluminum in diethyl ether. The reaction mixture is stirred for one hour after warming at room temperature. After careful addition of 20 ml of water, the ethereal phase is decanted off. The aqueous phase is shaken out three times with 20 ml of diethyl ether. The combined organic extracts are dried over anhydrous sodium sulfate. After removal of the solvent, 1.5 g of a compound of the formula: Me ₂ PtPt [P (-O-4-nonylphenyl) ₃ ] ₂

Preparation of the catalyst 9

To 2.0 g of a suspension of catalyst 5 in 30 ml of abs. Diethyl ether 7.2 ml of a 2.0 molar solution of methyllithium diethyl ether are added at -20 ° C. The reaction mixture is heated Stirred for one hour at room temperature. After careful addition of 20 ml of water, the ethereal phase is decanted off. The aqueous phase is shaken out three times with 20 ml of diethyl ether. The combined organic extracts are dried over anhydrous sodium sulfate. After removal of the solvent, 1.7 g of a compound of the formula are obtained: Me ₂ PtP (-O-2,4-di-tert-butylphenyl) ₃ ] ₂

Preparation of the catalyst 10

To 2.0 g of a suspension of catalyst 5 in 30 ml of abs. Diethyl ether are added at -20 ° C 7.2 ml of a 2.0 molar solution of butyllithium diethyl ether. The reaction mixture after heating for one hour at room temperature. After careful addition of 20 ml of water, the ethereal phase is decanted off. The aqueous phase is shaken out three times with 20 ml of diethyl ether. The combined organic extracts are dried over anhydrous sodium sulfate. After removal of the solvent, 2.1 g of a compound of the formula are obtained: Butyl ₂ PtP (-O-2,4-di-tert-butylphenyl) ₃ ] ₂

example 1

General Procedure: 50.0 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 20 Pa · s, inhibitor and 1.0 g of SiH crosslinker was mixed with the aid of a stirrer Company Janke & Kunkel IKA laboratory technology, type RE 162 homogeneously mixed, wherein the SiH crosslinker a copolymer of dimethylsiloxy and methylhydrogensiloxy and trimethylsiloxy units having a viscosity of 330 mPa · s and a content of Si-bonded hydrogen of 0.46 wt%. Subsequently, 10 ppm platinum complex (based on Pt) dissolved in 0.5 ml of dichloromethane, was added and stirred at room temperature.

In Example 1 was 3 mg of 1-ethynyl-1-cyclohexanol (ECH) as inhibitor component and 3.2 mg Catalyst 1 (equivalent to 10 ppm Pt).

Example 2

The The procedure described in Example 1 is repeated with the Difference that as an inhibitor component 20.0 mg of 2-phenyl-3-butyn-2-ol be used. For this purpose, 3.2 mg of catalyst 1 are stirred.

Example 3

The The procedure described in Example 1 is repeated with the Difference that used as inhibitor 3 mg diethyl maleate become. For this purpose, 3.2 mg of catalyst 1 are stirred.

Example 4

The The procedure described in Example 1 is repeated with the Difference that as the inhibitor component a combination of 2.0 mg of tris (2,4-di-tert-butylphenyl) phosphite and 2.0 mg of diethyl maleate becomes. For this purpose, 3.2 mg of catalyst 1 are stirred.

Example 5

The The procedure described in Example 1 is repeated with the Difference that as the inhibitor component is a combination of 1.0 mg tris (2,4-di-tert-butylphenyl) phosphite and 1.0 mg diethyl maleate used becomes. For this purpose, 4.3 mg of catalyst 2 are stirred.

Example 6

The The procedure described in Example 1 is repeated with the Difference that 3 mg ECH are used as inhibitor component. For this purpose, 5.0 mg of catalyst 3 are stirred.

Example 7

The The procedure described in Example 1 is repeated with the Difference that as the inhibitor component is a combination of 1.0 mg tris (2,4-di-tert-butylphenyl) phosphite and 1.0 mg diethyl maleate used becomes. For this purpose, 3.9 mg of catalyst 4 are stirred.

Example 8

The The procedure described in Example 1 is repeated with the Difference that as the inhibitor component is a combination of 1.0 mg tris (2,4-di-tert-butylphenyl) phosphite and 1.0 mg diethyl maleate used becomes. 4.1 mg of catalyst 5 are stirred in for this purpose.

Example 9

The The procedure described in Example 1 is repeated with the Difference that 3 mg ECH are used as inhibitor component. For this purpose, 3.3 mg of catalyst 6 are stirred.

Example 10

The The procedure described in Example 1 is repeated with the Difference that 3 mg ECH are used as inhibitor component. For this purpose, 3.6 mg of catalyst 7 are stirred.

Example 11

The The procedure described in Example 1 is repeated with the Difference that 3 mg ECH are used as inhibitor component. For this purpose, 3.8 mg of catalyst 8 are stirred.

Example 12

The The procedure described in Example 1 is repeated with the Difference that as the inhibitor component is a combination of 1.0 mg tris (2,4-di-tert-butylphenyl) phosphite and 1.0 mg diethyl maleate used becomes. For this purpose, 3.8 mg of catalyst 9 are stirred.

Comparative Example 1

When Comparative example is crosslinking with a platinum divinyl tetramethylsiloxane complex (1), despite the addition of inhibiting substances how ECH has a short pot life of less than one day at 50 ° C.

The pot lives were determined by visual assessment of a low-viscosity model formulation, the light-off temperatures are dependent on the chosen method parameters and were using a DIN53529T3 determined method.

Bsp

Beispiel

Kat

Katalysator

Inh

Inhibitor

ECH

1-Ethinyl-1-cyclohexanol

Temp

Anspringtemperatur

Δt

Topfzeit bei 50°C

Kat 0

Platindivinyltetramethylsiloxan-Komplex, „Karstedt-Kat"

Vgl 1

Vergleichsbeispiel 1

The following abbreviations are used:

Example

example

Kat

catalyst

inh

inhibitor

ECH

1-ethynyl-1-cyclohexanol

Temp

off temperature

.delta.t

Pot life at 50 ° C

Cat 0

Platinum divinyltetramethylsiloxane complex, "Karstedt-Kat"

Compare 1

Comparative Example 1

In Table 1 are the light-off temperatures and pot lives of the examples 1-10 and the comparative example.

It showed that a pot life of at least 2 days could be achieved. Table 1 Example Kat inh Temp .delta.t Compare 1 0 1-ethynyl-1-cyclohexanol 103 <1 day 2 1 1-ethynyl-1-cyclohexanol 119 4 days 3 1 2-phenyl-3-butyn-2-ol 125 3 days 4 1 diethyl maleate 120 2 days 5 1 Tris (2,4-di-tert-butylphenyl) phosphite, diethyl maleate 119 > 6 days 6 2 Tris (2,4-di-tert-butylphenyl) phosphite, diethyl maleate 148 > 6 days 7 3 1-ethynyl-1-cyclohexanol 144 4 days 8th 4 Tris (2,4-di-tert-butylphenyl) phosphite diethyl maleate 133 > 6 days 9 5 Tris (2,4-di-tert-butylphenyl) phosphite diethyl maleate 118 > 6 days 10 6 1-ethynyl-1-cyclohexanol 159 > 6 days 11 7 1-ethynyl-1-cyclohexanol 124 5 days

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 3723567 A [0005]
• - US 5270422 A [0005]
• EP 0761759 A2 [0005]
• DE 19757221 A1 [0005]
• US 4329275 A [0005]
• EP 1437382 A1 [0005]
• EP 0459464 A2 [0006]
• US 6252028 B [0007]
• US 6359098 B [0007]
• - US 4256616 A [0007]
• WO 03/098890 A1 [0007]

Cited non-patent literature

• - DIN53529T3 [0099]

Claims (9)

Platinum catalyst (D) of general formula (I), R ¹ ₂ Pt [P (OR ² ₃ ) ₃ ] ₂ (I) wherein R ¹ inde pendently of one another, identical or different, a - halogen, - simply negative inorganic radical, - CR ³ ₃ with R ³ inde pendent of each other, identically or differently a H, linear or branched aliphatic radicals having 1 to 18 carbon atoms, arylalkyl radicals with 6 to 31 carbon atoms - OR ³ wherein R ³ carries the abovementioned meaning, - SiR ³ ₃ where R ^{3 has} the abovementioned meaning, R ² independently of one another, identically or differently, an - alkyl of the formulas C _n H _{2n + 1} with n = 5-18 or C _m H _2m-1 with m = 5-31, - arylalkyl of the formula - (C ₆ H _5-p ) - (C _o H _{2o + 1} ) _p with o = 1-31 and p = 1-5, wherein the hydrogen atoms of the compounds mentioned above for R ¹ and R ² are substituted or unsubstituted by the groups -NH ₂ , -COOH, -F, -Br, -Cl, -aryl or -alkyl. Use of the platinum catalyst according to claim 1 as a catalyst for hydrosilylation reactions, for the hydrogenation of unsaturated organic compounds or Polymers and for the oligomerization of alkynes. Addition-crosslinking silicone compositions selected from the group containing - at least one each Compound (A), (B) and (D), - at least each a compound (C) and (D), and - at least each a compound (A), (B), (C) and (D) wherein (A) an organic A compound or an organosilicon compound containing at least two radicals with aliphatic carbon-carbon multiple bonds, (B) an organosilicon compound containing at least two Si-bonded ones Hydrogen atoms, (C) an organosilicon compound containing SiC-bonded radicals with aliphatic carbon-carbon multiple bonds and Si-bonded hydrogen atoms, and (D) a platinum catalyst mean, thereby characterized in that the platinum catalyst (D) is a platinum catalyst according to claim 1. Addition-crosslinking silicone compositions according to claim 3, characterized in that they are inhibitors as further component (E) or stabilizers or a mixture of at least two components (E) in an amount of 0.00001% to 5% by total weight of the composition. Addition-crosslinking silicone compositions according to one of claims 3 or 4, characterized in that they as further component (F), selected from the Group containing reinforcing and non-reinforcing Fillers, dispersing aids, solvents, Adhesion promoters, pigments, dyes, plasticizers, organic polymers, Heat stabilizers, fungicides, fragrances, rheological additives, corrosion inhibitors, Oxidation inhibitors, light stabilizers, flame retardants Means and means for influencing the electrical properties. Addition-crosslinking silicone compositions according to one of claims 3 to 5, characterized in that they as further constituent at least one addition-crosslinking Catalysts (G) included. Process for the preparation of an addition-curing Silicone compositions according to any one of claims 3 to 6, characterized in that - at least each a compound (A), (B) and (D), - at least each a compound (C) and (D), or - at least each a compound (A), (B), (C) and (D) are mixed together. Process according to claim 7, characterized characterized in that in each case additionally further connections from the group of compounds containing (E), (F), (G) mixed become. Use of the composition according to one of claims 3 to 6 for the production of moldings, for silicone coating, for impregnation, for the production of impressions, for sealing embedding and Casting applications.